EP0027157B1 - Verfahren zur selektiven Dealkylierung alkyl-substituierter aromatischer Kohlenwasserstoffe - Google Patents

Verfahren zur selektiven Dealkylierung alkyl-substituierter aromatischer Kohlenwasserstoffe Download PDF

Info

Publication number
EP0027157B1
EP0027157B1 EP80102348A EP80102348A EP0027157B1 EP 0027157 B1 EP0027157 B1 EP 0027157B1 EP 80102348 A EP80102348 A EP 80102348A EP 80102348 A EP80102348 A EP 80102348A EP 0027157 B1 EP0027157 B1 EP 0027157B1
Authority
EP
European Patent Office
Prior art keywords
catalyst
alkyl
dealkylation
substituted aromatic
hydrocarbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80102348A
Other languages
English (en)
French (fr)
Other versions
EP0027157A1 (de
EP0027157B2 (de
Inventor
Tamio Onodera
Tokuji Sakai
Yasuo Yamasaki
Koji Sumitani
Minekazu Sueoka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Petrochemical Industries Ltd
Original Assignee
Teijin Petrochemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=14795409&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0027157(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Teijin Petrochemical Industries Ltd filed Critical Teijin Petrochemical Industries Ltd
Publication of EP0027157A1 publication Critical patent/EP0027157A1/de
Application granted granted Critical
Publication of EP0027157B1 publication Critical patent/EP0027157B1/de
Publication of EP0027157B2 publication Critical patent/EP0027157B2/de
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
    • C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
    • C07C4/18—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (14)

1. Verfahren zur Dealkylierung eines Kohlenwasserstoffmaterials mit einem Gehalt von wenigstens einem alkylsubstitutierten aromatischen Kohlenwasserstoff, welcher wenigstens eine Alkylgruppe mit mindestens zwei Kohlenstoffatomen an den aromatischen Ring gebunden aufweist, in der Gasphase in Gegenwart von Wasserstoff unter Verwendung eines Hydrodealkylierungskatalysators, dadurch gekennzeichnet, daß
(a) der Hydrodealkylierungskatalysator aus einem kristallinen Aluminosilicat mit einem Kieselsäure/Aluminiumoxyd-Molverhältnis von 20 bis 200 besteht, das hauptsächlich in der H-Form vorliegt und ein Edelmetal 1 aus der Gruppe von Platin, Palladium, Rhodium und Iridium enthält, und
(b) die Dealkylierung bei einer Temperatur von 250°C bis 420°C und einem Druck von nicht mehr als 7,9 bar ausgeführt wird, wodurch die wenigstens zwei Kohlenstoffatome enthaltende Alkylgruppe selektiv von dem alkylsubstitutierten aromatischen Kohlenwasserstoff entfernt wird.
2. Verfahren nach Anspruch 1, worin das kristalline Aluminosilicat ein Kieselsäure/Aluminiumoxyd-Molverhältnis von 30 bis 150 aufweist.
3. Verfahren nach Anspruch 1, worin das kristalline Aluminosilicat Zeolith ZSM-5 ist.
4. Verfahren nach Anspruch 1, worin der Katalysator 0,005 bis 1 Gew.%, bezogen auf das genannte kristalline Aluminosilicat, des genannten Edelmetalls enthält.
5. Verfahren nach Anspruch 1, worin die Dealkylierung bei einer Temperatur von 320 bis 410°C ausgeführt wird.
6. Verfahren nach Anspruch 1, worin die Dealkylierung unter einem Druck von 1,01 bis 7,22 bar ausgeführt wird.
7. Verfahren nach Anspruch 1, worin das Kohlenwasserstoffmaterial bei einer stündlichen Raumströmungsgeschwindigkeit auf Gewichtsbasis von etwa 0,1 bis etwa 20 zugefürt wird.
8. Verfahren nach Anspruch 1, worin das Kohlenwasserstoffmaterial und Wasserstoff so zugeführt werden, daß das Molverhältnis von Wasserstoff zu Kohlenwasserstoffmaterial im Bereich von 0,5 bis 10 liegt.
9. Verfahren nach Anspruch 1, worin der alkylsubstituierte aromatische Kohlenwasserstoff ein aromatischer Kohlenwasserstoff ist, der an den aromatischen Ring 1 bis 3 lineare oder verzweigte Alkylgruppen mit 2 bis 4 Kohlenstoffatomen und gegebenenfalls 1 bis 5 an den aromatischen Ring gebundene Methylgruppen aufweist.
10. Verfahren nach Anspruch 9, worin der alkylsubstituierte aromatische Kohlenwasserstoff aus der Gruppe von Äthylbenzol, Äthyltoluol, Diäthylbenzol, Äthylxylol, n-Propylbenzol, Cumol und Cymol gewählt ist.
11. Verfahren nach Anspruch 1, worin das Kohlenwasserstoffmaterial ein Gemisch von dem genannten alkylsubstituierten aromatischen Kohlenwasserstoff und einem methylsubstituierten aromatischen Kohlenwasserstoff umfaßt.
12. Verfahren nach Anspruch 11, worin das Kohlenwasserstoffmaterial wenigstens 80 Gew.% des genannten Gemisches von aromatischen Kohlenwasserstoffen enthält.
13. Verfahren nach Anspruch 11, worin der genannte methylsubstituierte aromatische Kohlenwasserstoff ein methylsubstituiertes Benzol mit 1 bis 5 an den Benzolring gebundenen Methylgruppen ist.
14. Verfahren nach Anspruch 1, worin das Kohlenwasserstoffmaterial wenigstens 30 Gew.% des genannten alkylsubstituierten aromatischen Kohlenwasserstoffes enthält.
EP80102348A 1979-09-21 1980-04-30 Verfahren zur selektiven Dealkylierung alkyl-substituierter aromatischer Kohlenwasserstoffe Expired EP0027157B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP120805/79 1979-09-21
JP12080579A JPS5645422A (en) 1979-09-21 1979-09-21 Selective dealkylation process

Publications (3)

Publication Number Publication Date
EP0027157A1 EP0027157A1 (de) 1981-04-22
EP0027157B1 true EP0027157B1 (de) 1983-11-16
EP0027157B2 EP0027157B2 (de) 1989-02-01

Family

ID=14795409

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80102348A Expired EP0027157B2 (de) 1979-09-21 1980-04-30 Verfahren zur selektiven Dealkylierung alkyl-substituierter aromatischer Kohlenwasserstoffe

Country Status (4)

Country Link
US (1) US4320242A (de)
EP (1) EP0027157B2 (de)
JP (1) JPS5645422A (de)
DE (1) DE3065587D1 (de)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4577049A (en) * 1980-03-26 1986-03-18 Mobil Oil Corporation Alkylation of durene utilizing high boiling condensed polyaromatic compounds
US4560820A (en) * 1981-04-13 1985-12-24 Chevron Research Company Alkylaromatic dealkylation
JPS5910530A (ja) * 1982-06-18 1984-01-20 モービル・オイル・コーポレーション 重質芳香族原料の転化方法
JPS60246330A (ja) * 1984-05-21 1985-12-06 Idemitsu Petrochem Co Ltd ベンゼンおよびメチル置換ベンゼンの製造方法
JPS6147425A (ja) * 1984-08-10 1986-03-07 Sumitomo Chem Co Ltd パラ選択的脱アルキル化方法
JPS6168319A (ja) * 1984-09-10 1986-04-08 Asahi Chem Ind Co Ltd 結晶性アルミノシリケ−トの合成法
US5004854A (en) * 1986-12-04 1991-04-02 Mobil Oil Corp. Pseudocumene and mesitylene production and coproduction thereof with xylene
US5004855A (en) * 1987-08-25 1991-04-02 Toray Industries, Inc. Process for conversion of ethylbenzene in C8 aromatic hydrocarbon mixture
US5053573A (en) * 1990-09-14 1991-10-01 Mobil Oil Corporation Reduction of benzene content of reformate by reaction with cycle oils
US5082983A (en) * 1990-09-14 1992-01-21 Mobil Oil Corporation Reduction of benzene content of reformate in a catalytic cracking unit
JP2970683B2 (ja) * 1990-10-12 1999-11-02 日石三菱株式会社 水素化脱アルキル触媒を用いた水素化脱アルキル法
USH1723H (en) * 1992-09-11 1998-04-07 Leuenberger; Ernest L. Process for producing gasoline blending components from jet range and heavier aromatics
US5552132A (en) * 1994-10-28 1996-09-03 Chevron U.S.A. Inc. Preparing a crystalline aluminophosphate composition
US6060417A (en) * 1996-06-28 2000-05-09 Toray Industries, Inc. Catalyst composition for transalkylation of alkylaromatic hydrocarbons and process for production of xylene
US5962758A (en) * 1998-04-09 1999-10-05 Abb Lummus Global Inc. Process of producing ethylbenzene using alkylation and transalkylation with propylbenzene destruction
US7553791B2 (en) * 2002-11-14 2009-06-30 Exxonmobil Chemical Patents Inc. Heavy aromatics conversion catalyst composition and processes therefor and therewith
DE602008005752D1 (de) * 2007-08-22 2011-05-05 Exxonmobil Chem Patents Inc Verfahren zur herstellung von sec.-butylbenzol
WO2010042269A1 (en) * 2008-10-10 2010-04-15 Exxonmobil Chemical Patents Inc. Process for producing phenol and methyl ethyl ketone
KR101369345B1 (ko) 2011-12-22 2014-03-06 인하대학교 산학협력단 바이모달 세공구조의 탈알킬화 촉매를 이용한 알킬치환된 ｃ９＋ 방향족 화합물의 선택적 저온 탈알킬화 방법
WO2016081082A1 (en) * 2014-11-20 2016-05-26 Exxonmobil Chemical Patents Inc. Conversion of lignin to fuels and aromatics
WO2017032672A1 (en) * 2015-08-21 2017-03-02 Sabic Global Technologies B.V. Process for producing btx from a c5-c12 hydrocarbon mixture
FR3069244B1 (fr) * 2017-07-20 2020-03-06 IFP Energies Nouvelles Procede d’hydrogenolyse pour une production amelioree de paraxylene
WO2021126437A1 (en) * 2019-12-19 2021-06-24 Exxonmobil Chemical Patents Inc. Aikyl-demethylation processes and catalyst compositions therefor
US20230023923A1 (en) * 2019-12-19 2023-01-26 Exxonmobil Chemical Patents Inc. Alkyl-Demethylation Processes and Catalyst Compositions Therefor
US11028329B1 (en) 2020-04-10 2021-06-08 Saudi Arabian Oil Company Producing C6-C8 aromatics from FCC heavy naphtha

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1389499A (fr) * 1962-12-12 1965-02-19 British Petroleum Co Procédé de désalcoylation, notamment de mélanges d'hydrocarbures
AT256069B (de) * 1963-05-31 1967-08-10 Union Carbide Corp Verfahren zur Desalkylierung alkylaromatischer Kohlenwasserstoffe
FR2254542B1 (de) * 1973-12-13 1976-05-14 Inst Francais Du Petrole
US3948758A (en) * 1974-06-17 1976-04-06 Mobil Oil Corporation Production of alkyl aromatic hydrocarbons
US3945913A (en) * 1974-08-26 1976-03-23 Mobil Oil Corporation Manufacture of lower aromatic compounds
DE2558035A1 (de) * 1975-12-22 1977-06-23 Mobil Oil Corp Kombiniertes verfahren zur katalytischen umwandlung und hydrodealkylierung von kohlenwasserstoffen
FR2367035A1 (fr) * 1976-10-11 1978-05-05 Pro Catalyse Procede d'hydrodealkylation d'hydrocarbures alkyl aromatiques en presence d'un catalyseur ayant un support de type aluminate
US4101595A (en) * 1977-05-02 1978-07-18 Mobil Oil Corporation Conversion of ethyl benzene to para xylene

Also Published As

Publication number Publication date
EP0027157A1 (de) 1981-04-22
US4320242A (en) 1982-03-16
EP0027157B2 (de) 1989-02-01
DE3065587D1 (en) 1983-12-22
JPS5645422A (en) 1981-04-25

Similar Documents

Publication Publication Date Title
EP0027157B1 (de) Verfahren zur selektiven Dealkylierung alkyl-substituierter aromatischer Kohlenwasserstoffe
US5968342A (en) Zeolite catalyst and method of converting hydrocarbons using the same
EP0018498B1 (de) Isomerisierung von Xylol
US5866744A (en) Process for converting a c9 + hydrocarbon to a C6 to C8 aromatic using a steamed, acid-leached, impregnated zeolite
KR101162796B1 (ko) 여러고리 방향족 화합물의 크실렌으로의 촉매 전환
EP0045054B1 (de) Verfahren zur Herstellung von p-Xylol
US5952536A (en) Aromatics and toluene/trimethylbenzene gas phase transalkylation processes
EP0772492B1 (de) Para-xylen selektives reformieren/aromatisieren
US5866741A (en) Transalkylation/hydrodealkylation of a C9 + aromatic compounds with a zeolite
US5804059A (en) Process of preparing a C6 to C8 hydrocarbon with a steamed, acid-leached, molybdenum containing mordenite catalyst
US5004854A (en) Pseudocumene and mesitylene production and coproduction thereof with xylene
US3843740A (en) Production of aromatics
JP2970683B2 (ja) 水素化脱アルキル触媒を用いた水素化脱アルキル法
US5032561A (en) Catalyst composition for cracking non-aromatic hydrocarbons and isomerizing C8-aromatic hydrocarbons
EP0045333B1 (de) Verfahren zum Isomerisieren von Xylolen
AU718155B2 (en) Selective catalytic conversion of a C9 aromatic feedstock containing substantial amounts of ethyl substituted aromatic components to a product rich in toluene and/or xylenes
US3873632A (en) Alkylaromatic hydrocarbon isomerization process
US5929295A (en) Hydrodealkylation and transalkylation of C9 + aromatic compounds
US5698757A (en) Hydrodealkylation catalyst composition and process therewith
JPH0244582B2 (de)
EP1040089B1 (de) Herstellungsverfahren für meta-xylol
US5089459A (en) Catalyst composition, process for cracking non-aromatic hydrocarbons and process for isomerizing c8 aromatic hydrocarbons
EP0043695A1 (de) Aktivierung eines Aluminiumsilikatkatalysators, der mittels Ionentausch eingetauschte Galliumionen enthält
US5177287A (en) Catalyst composition, process for cracking non-aromatic hydrocarbons and process for isomerizing C8 aromatic hydrocarbons
JPS6022932A (ja) 触媒組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19801128

AK Designated contracting states

Designated state(s): DE FR GB IT NL

ITF It: translation for a ep patent filed

Owner name: BARZANO' E ZANARDO MILANO S.P.A.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB IT NL

REF Corresponds to:

Ref document number: 3065587

Country of ref document: DE

Date of ref document: 19831222

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: MOBIL OIL CORPORATION

Effective date: 19840813

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19890201

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE FR GB IT NL

ITF It: translation for a ep patent filed

Owner name: BARZANO' E ZANARDO MILANO S.P.A.

ET3 Fr: translation filed ** decision concerning opposition
NLR2 Nl: decision of opposition
NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19980320

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19980326

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980414

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980630

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991231

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19991101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000201